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Alkanes-assisted low temperature formation of highly ordered SBA-15
with large cylindrical mesopores{
Junming Sun,a He Zhang,a Ding Ma,a Yangying Chen,a Xinhe Bao,*a Achim Klein-Hoffmann,b
Norbert Pfänderb and Dang Sheng Sub
Received (in Cambridge, UK) 8th July 2005, Accepted 31st August 2005
First published as an Advance Article on the web 27th September 2005
DOI: 10.1039/b509713d
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Highly ordered SBA-15 silicas with large cylindrical mesopores
(y15 nm) are successfully obtained with the help of NH4F by
controlling the initial reaction temperatures in the presence of
excess amounts of alkanes.
With the discovery of M41s,1 great efforts have been made on the
construction of texture controllable mesoporous materials. Among
them, tailoring the pore size of the mesoporous materials has been
one of the hot issues for the purpose of providing a good
performance for specific applications, such as the adsorption/
separation of bulky molecules, the immobilization of enzymes as
well as the catalytic transformation reactions of macromolecules,
etc. Methods to modify the pore size of the mesoporous materials
include the post synthesis treatment,2 using different surfactant
molecules (template) with different chain lengths3 and employing
organic solvents as swelling agents.4 The addition of swelling
agents, such as TMB, alkanes,5,6 has been proved to be the most
effective way in expanding the pore size of MCM-41 silicas (2–
10 nm). Recently, the nonionic triblock copolymers templated
SBA-15 silicas have attracted great interests due to their larger
pores, thicker pore walls and therefore higher hydrothermal
stabilities.7 Meanwhile, the pore size of SBA-15 could be tuned in
the range of 7–30 nm by using TMB as expander. However,
extensive studies show that a phase transition from highly ordered
SBA-15 (7–12 nm) to mesoporous cellular foams (MCF) with
large nodded pore structures (y22–42 nm) occurred with
increasing amounts of TMB.8 Therefore, it is still essential to find
other methods of tuning the pore size of highly ordered
mesoporous materials. In other works, organic auxiliary chemicals
(e.g., DMF,9 alkanes10,11) have also been investigated.
Unfortunately, the maximum pore size of the highly ordered
SBA-15 is only ca. 12 nm (with decane). Furthermore, when
alkanes with shorter chain length (such as nonane, octane, etc.)
were employed, disordered MCF silicas were produced under the
temporal reaction conditions.10 Up to now, to our knowledge, the
synthesis of highly ordered SBA-15 silicas with cylindrical pore
sizes larger than 12 nm has rarely been reported. Herein, it is
demonstrated for the first time that the pore size of highly ordered
SBA-15 could be continuously expanded to y15 nm by carefully
a
State Key Laboratory of Catalysis, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China.
E-mail: xhbao@dicp.ac.cn; Fax: +86-411-84694447
b
Department of Inorganic Chemistry, Fritz-Haber Institute of the Max
Planck Society, Berlin D-14195, Germany
{ Electronic supplementary information (ESI) available: Fig. S1 N2
adsorption–desorption isotherms of the samples prepared with (a) C6; (b)
C7; (c) C9. See http://dx.doi.org/10.1039/b509713d
This journal is ß The Royal Society of Chemistry 2005
controlling the initial reaction temperatures with excess amounts of
alkanes (from nonane to hexane). To our knowledge, it is the
largest cylindrical mesopore diameter with regard to highly
ordered SBA-15 silicas.
As a typical synthesis procedure, 2.4 g of EO20PO70EO20 (P123)
was dissolved in 84 ml HCl solution (1.30 M), followed by the
addition of 0.027 g of NH4F. The mixture was then stirred at 288 K
to yield a clear solution. Different alkanes (with a constant
alkane/P123 molar ratio of y240) and 5.5 ml TEOS were
premixed and then introduced into the solution under stirring. The
above mixture was stirred at a given temperature for 20 h, and
then transferred into an autoclave for further reaction at 373 K for
48 h. The products were collected by filtration, dried in air, and
calcined at 813 K for 5 h to remove the templates. The highly
ordered SBA-15 silicas with large cylindrical pores were thus
obtained.
Various alkanes from nonane to hexane have been investigated
at different initial reaction temperatures. It is found that when
proper reaction temperatures are employed (Table 1), all the
obtained materials have highly ordered mesoporous structures.
Fig. 1 (top) gives the SAXD (Small Angle X-ray diffractions)
patterns of the calcined samples prepared with different alkanes.
All samples show four well-resolved peaks that can be indexed as
(100), (110), (200), (210) diffractions, indicating a well-ordered
hexagonal mesostructure of the obtained materials. Furthermore,
the interplanar spacing d100 increases continuously with the
decrease of the alkane chain length, indicating a continuous
expansion of the pore size of the obtained SBA-15. When excess
amounts of hexane are used, the obtained sample exhibits a d100
spacing of 14.2 nm (vs. 12.3 nm with nonane), and the calculated
hexagonal unit cell value (a0 5 2d100/31/2) of the sample from (100)
diffraction peak reaches ca. 16.4 nm. Data concerning the physical
properties of the samples are shown in Table 1.
N2 adsorption–desorption isotherms of the obtained samples
yield type IV isotherms with H1-type hysteresis at the relative
pressure of 0.8–0.9, which is characteristic for mesoporous
materials with cylindrical channels in hexagonal arrangement
(ESI{, Fig. S1). From the N2 adsorption isotherms, one can
observe that the capillary condensation step shifts to the higher
relative pressure with the decrease of the alkane chain length. Fig. 1
(bottom) shows the pore size distributions of the obtained samples
calculated from the adsortion branches. It is clear that the pore size
increases with the decrease of the alkane chain length, which is
consistent with the XRD results. The pore size of SBA-15 prepared
with hexane can reach ca. 15 nm. At the same time, the BET
surface area and pore volume of the sample are 614 m2 g21 and
Chem. Commun., 2005, 5343–5345 | 5343

Table 1 Physical data concerning the samples prepared with different alkanes
Alkanes Initial reaction temperature/K d100 spacing/nm Unit cell (a0)a/nm
Nonane 300 12.3 14.2
Heptane 295 13.4 15.5
Hexane 290 14.2 16.4
a b
Calculated from (100) diffraction peak of the corresponding SAXD pattern.
desorption isotherms of the corresponding sample.
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Fig. 1 SAXD patterns (top) and pore size distributions (bottom) of the
samples prepared with (a) nonane, (b) heptane, (c) hexane. The pore size
distributions were calculated from the adsorption branches.
1.40 cc g21, respectively. To our knowledge, this is the largest
cylindrical pore diameter of all the reported highly ordered
mesoporous SBA-15.
Fig. 2 gives the TEM images of the obtained materials prepared
with hexane. The TEM image in Fig. 2a clearly shows the highly
ordered parallel cylindrical pore channels. The width of a unit cell
judged from the cross-sectioned TEM image (Fig. 2b) is ca. 16 nm,
which is in agreement with the results of the SAXD. It is also
Fig. 2 TEM images of the sample prepared with hexane: (a) taken
vertical to the parallel channels; (b) along the parallel channels.
5344 | Chem. Commun., 2005, 5343–5345
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Pore diameterb/nm Surface areas/m2 g21
13.4 637
15.0 620
15.7 614
Calculated from the adsorption branch of the N2 adsorption–
concluded by TEM/SAXD that the products obtained before
hydrothermal treatments are also highly ordered mesoporous
materials, however, the crystallinity is lower than it is after
hydrothermal treatment.
Initial reaction temperature plays a key role in the synthesis of
highly ordered SBA-15 in the presence of alkanes. It was reported
that those SBA-15 materials prepared with short chain alkanes
such as nonane or octane were always disordered large-pore
mesoporous cellular foams (MCF) under the temporal synthesis
conditions.10 In the present study, highly ordered SBA-15 with
large cylindrical mesopores is successfully prepared with such short
chain alkanes by finely controlling the initial reaction temperature.
For each alkane, there is a temperature when there is a phase
transition from highly ordered mesoporous structure to disordered
one (e.g. MCF). For example, in the case of hexane, the reaction
temperature should be strictly lower than 290 K. Otherwise, other
structures (such as, MCF materials) would form. In the case of
heptane and nonane, the initial temperature should be lower than
295 K and 300 K, respectively. This indicates that the reaction
temperature used in the current study depends strongly on the
chain length of the alkanes (Table 1) in order to obtain highly-
ordered SBA-15 silicas, i.e., the shorter the chain length of alkanes,
the lower the reaction temperature should be chosen. However,
when the initial reaction temperature is lower than 283 K, only
amorphous silica gels are obtained for all alkanes. Therefore, the
preparation of highly ordered materials is carried out in a specific
temperature range for each alkane. Within this range, a higher
temperature on the initial reaction stage will lead to a slight shift of
the (100) diffraction peaks to lower angles, indicating a slight
increase of the pore size of the obtained SBA-15.7 The synthesis
reaction temperatures we chose (see Table 1) are close to but below
the corresponding phase transition temperatures.
From Table 1, it shows that the shorter the alkane chain, the
larger the pore diameter would be. The pore size expansion
tendency is obviously different from that of MCM-41. In the case
of MCM-41, where the traditional cationic surfactant was used,
the pore size would enlarge with the increase of alkane chain
length.5,6 This is possibly related to the nature of the interactions
between different surfactants and alkanes. It is well known that the
nonionc copolymer surfactants (e.g. P123 in the current case) have
a large number of monomers blocks and therefore can have many
configurations. The solubilization behavior of different alkanes in
the hydrophobic microdomains, which can lead to the dilution of
PPO blocks and swelling of nonionic copolymer micelles, has been
studied extensively.12 It has been found that, with the decrease of
alkane chain length, the solubilization capacity of alkanes in
hydrophobic core of P123 surfactant increases, i.e., the shorter the
alkane chain length is, and the more the alkanes would be
accommodated in the micelles cores, which results in larger swollen
micelles dimension. Therefore, it can be concluded that, in the
This journal is ß The Royal Society of Chemistry 2005

present situation, the higher solubilization capacity of shorter
chain length alkanes (such as hexane) determines the ultimate
larger pore diameter of SBA-15 silicas. In addition, at relatively
higher initial reaction temperatures (such as in the case of hexane,
higher than 290 K), disordered mesostructures (e.g., MCF) are
obtained, which may also be related to the solubilization behavior
of alkanes.
On the other hand, the effect of inorganic salts (ion strength) on
the organization behavior of nonionic surfactants has been widely
studied,13 and the synthesis temperature of SBA-15 has been
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decreased considerably with the addition of a proper amount of
inorganic salts.14 In the current P123 templated system, it is found
that, without alkanes, the products prepared at 290 K are just
amorphous silica gels even in the presence of NH4F, indicating
that it is the existence of alkanes other than inorganic salts that
plays the key role in the organization of the hybrid composites at
low temperature. Meanwhile, with alkanes, disordered meso-
porous materials would be formed in the absence of fluoride at
290 K, confirming that the addition of fluoride can improve the
ordering of obtained mesoporous materials.11 Moreover, it is
reported that the PPO moieties of the P123 show increasing
hydrophilic tendency with the decrease of temperatures, which
results in no aggregation of surfactants at lower temperatures.15
Therefore, the condensation of the inorganic–organic hybrid
surfactant monomers at relatively lower temperatures, i.e. room
temperature, often leads to amorphous silica gel.7 The hydro-
phobic PPO blocks have been reported to be mainly responsible
for the micellization.16 At the low temperature, the PPO blocks are
easily hydrated and exhibit a certain degree of hydrophilic
property and lead to the increase of critical micelle concentration
(c.m.c.) of the P123 surfactants, and thus fail to serve as the
template for mesoporous SBA-15.15 In the current case, we
propose that the doping of PPO blocks with alkanes may suppress
the hydration of the hydrophobic PPO blocks, and therefore the
corresponding c.m.c. of the surfactant is lower at low tempera-
tures. At the same time, the solubilization of alkanes in the PPO
blocks swells hydrophobic cores of the hybrid micelles. Highly
ordered SBA-15 silicas with large cylindrical pore size are thus
produced in the presence of a small amount of fluoride at the
relatively low temperatures.
Our results indicate that alkanes with shorter chain length (from
nonane to hexane) could be used as expanders to synthesize highly-
ordered large-pore SBA-15 silicas with the help of NH4F. It is
observed that in a certain range, the shorter the alkane chain
length, the larger the pore size of the obtained SBA-15 silicas. By
using this method, the largest pore size of the obtained SBA-15
with highly ordered cylindrical porous structure is about 15 nm.
Up to now, it is the largest cylindrical pore size among all the
highly ordered SBA-15 samples reported. The obtained materials
have potential applications in bulky macromolecular catalysis,
This journal is ß The Royal Society of Chemistry 2005
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separation of biomolecules as well as enzymes immobilization.
Detailed investigation on the temperature induced structure
transition by different alkanes is being processed.{§
We are grateful for the support of the National Natural Science
Foundation of China (No. 90206036) and the Ministry of
Science and Technology of China (G1999022406). Junming Sun
thanks Gang Hu (University of Oxford) for reading through the
paper.
Notes and references
{ XRD patterns were collected on a Rigaku D/MAX 2400 diffractometer
equipped with a CuKa X-ray source operating at 40 kV and 50 mA. The
N2 adsorption–desorption isotherms were recorded on an ASAP 2000
instrument.
§ The TEM images were obtained with a Philips CM 200 Transmission
Electron Microscope equipped with a CCD camera.
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